US20130265376A1 - Inkjet Compositions For Forming Functional Glaze Coatings - Google Patents
Inkjet Compositions For Forming Functional Glaze Coatings Download PDFInfo
- Publication number
- US20130265376A1 US20130265376A1 US13/911,107 US201313911107A US2013265376A1 US 20130265376 A1 US20130265376 A1 US 20130265376A1 US 201313911107 A US201313911107 A US 201313911107A US 2013265376 A1 US2013265376 A1 US 2013265376A1
- Authority
- US
- United States
- Prior art keywords
- inkjet composition
- composition according
- inkjet
- effect
- ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 115
- 238000000576 coating method Methods 0.000 title claims description 5
- 239000000919 ceramic Substances 0.000 claims abstract description 54
- 230000000694 effects Effects 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 239000011521 glass Substances 0.000 claims abstract description 17
- 239000002932 luster Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000010304 firing Methods 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 230000000149 penetrating effect Effects 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- LOUBVQKDBZRZNQ-UHFFFAOYSA-M [O-2].[O-2].[OH-].O.[V+5] Chemical compound [O-2].[O-2].[OH-].O.[V+5] LOUBVQKDBZRZNQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 238000007641 inkjet printing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 2
- 150000003682 vanadium compounds Chemical class 0.000 claims 4
- 239000000049 pigment Substances 0.000 abstract description 8
- 239000002270 dispersing agent Substances 0.000 description 22
- 239000000976 ink Substances 0.000 description 18
- 239000003085 diluting agent Substances 0.000 description 17
- 230000000704 physical effect Effects 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000003658 tungsten compounds Chemical class 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 229910004829 CaWO4 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- LJRUVLUNYJXTJJ-UHFFFAOYSA-N [Cr](=O)([O-])[O-].[Fe+2].[Zn+2].[Cr](=O)([O-])[O-] Chemical compound [Cr](=O)([O-])[O-].[Fe+2].[Zn+2].[Cr](=O)([O-])[O-] LJRUVLUNYJXTJJ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- JGKGEXCILSDQBF-UHFFFAOYSA-N chromium(3+);cobalt(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Cr+3].[Fe+3].[Co+2] JGKGEXCILSDQBF-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- -1 glycolethers Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- KHJHBFLMOSTPIC-UHFFFAOYSA-N prop-2-enylidenechromium Chemical compound C(=C)C=[Cr] KHJHBFLMOSTPIC-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
Definitions
- the present invention provides inkjet compositions that can be used to modify the physical properties of the surface of glass and ceramic substrates and thus provide a functional coating or glaze after firing.
- the present invention provides inkjet compositions that can be used to modify the physical properties of the surface of glass and ceramic substrates and thus provide a functional coating or glaze after firing.
- the physical properties of the ceramic article that can be changed or modified with the inkjet compositions of the present invention can affect various attributes of the ceramic article after firing, including: gloss, matt, contrast gloss (luster), specular reflection (metallic appearance), relief and slipperiness.
- the inkjet compositions according to the invention include solvents, additives for dispersion, and inorganic substances.
- the inorganic substances contained in the inkjet compositions are the responsible for the above mentioned effects on the surface of the ceramic article.
- the inorganic substance may be a specific frit, a crystalline oxide, or a combination of frits and crystalline oxides.
- the inkjet compositions of the present invention may be used in conjunction with a variety of substrates including, for example: ceramic tiles (e.g., floor tile, wall tile etc.); dinnerware; brick tiles; glass; enameled steel; enameled cast iron; and enameled aluminum.
- ceramic tiles e.g., floor tile, wall tile etc.
- dinnerware e.g., dinnerware
- brick tiles e.g., glass
- enameled steel e.g., enameled cast iron
- enameled aluminum e.g., aluminum
- FIG. 1 is a chart showing various inkjet technologies suitable for use with inkjet compositions according to the invention.
- FIG. 2 is a graph showing the X-ray characterization of a ceramic tile to which an ink composition according to the invention has been applied.
- Inkjet compositions according to the invention can be applied using inkjet decoration machines commonly used glazing lines of the above mentioned substrates. Also, inkjet plotter machines are commercially available, which permit the inkjet compositions to be used in a discontinuous way.
- Inkjet machines may be used in simple-pass or multi-pass operating mode.
- the simple-pass mode the inkjet print head makes only one-pass over the surface of the substrate.
- the multi-pass mode the inkjet print head makes more than one-pass over the surface of the substrate. In some cases, several passes are needed on order to achieve the desired properties.
- inkjet print head technologies are suitable for use with inkjet compositions according to the present invention.
- Drop-on-demand technology is the most commonly employed technology in the ceramic industry.
- Various inkjet technologies suitable for use with the present invention are shown in FIG. 1 .
- inkjet inks are utilized to provide coloration to the ceramic substrate when fired.
- conventional inkjet inks include solvents, dispersants and color-producing substances, which are typically ceramic pigments.
- the current ceramic pigments used in inkjet inks include zircon praseodymium yellow zircon, zinc iron chromite brown, cobalt aluminate blue, chrome tin pink sphene, iron cobalt chromite black spinel, etc.
- the inkjet compositions according to the present invention preferably do not contain any color-producing ceramic pigments. Instead, they contain inorganic substances that, although milled below 10 micron size so as to be capable of being ink-jet printable and being applied as very low deposits, are applied to modify targeted physical properties of the ceramic surface on which they are applied. Modification of the physical properties of the ceramic substrate can affect various attributes of the ceramic article after firing, including: gloss, matt, contrast gloss (luster), specular reflection (metallic appearance), relief and slipperiness.
- inkjet technology provides the advantage of being able to apply the inkjet compositions in a determined place with high accuracy. So, the change of physical properties of the surface of the tile may follow an accurate pattern, opening new possibilities for tile decoration. It is seen as an advantage to combine the application of inkjet compositions according to the invention with the conventional pigmented inkjet inks. In this way, the ceramic article may be fully decorated using inkjet technology.
- One object of the present invention is to develop a set of inkjet compositions having a completely distinct nature compared to current pigmented inkjet inks.
- Inkjet compositions according to the invention are capable of being applied using conventional inkjet printing equipment without clogging the spray nozzles.
- the preferable have appropriate physical properties, such as a viscosity within the range of from about 5 to about 50 mPa ⁇ s, a surface tension of from about 20 to about 40 mN/m, and a density of from about 0.8 to about 1.5 g/mL.
- the inkjet compositions according to the invention preferably exhibit little or no volatility, and are stable with the materials used to make inkjet printing systems (e.g., print heads, nozzles, delivery lines etc.).
- the inkjet compositions according to the invention work with the requirements of ceramic systems.
- they must be capable of developing the desired surface affect (i.e., the desired physical surface change) after firing.
- The must be capable of interacting with the glazed surface to become part of it.
- They must contain sufficient solids to allow reasonable productivity. And, they must allow for enough resolution despite the large amount to be deposited.
- the quantity of the inkjet compositions according to the invention deposited on the surface of the ceramic substrate will depend on the type of effect desired.
- the inkjet compositions according to the invention can be applied over a wide range of application rates, from about 5 up to about 500 g/m 2 , depending upon the desired affect. Typical application rates are used in the Examples below.
- the affects can be obtained using the disclosed inkjet compositions.
- the affects are provided mainly by the presence of a particular solid in the inkjet composition.
- the inkjet composition contains a solvent or diluent, a dispersant and the solid that creates the effect.
- the solid is dispersed in a solvent or diluent wherein the diluent is a single phase liquid comprising several solvents.
- This diluent can comprise aliphatic and/or aromatic hydrocarbon components as well as glycols, glycolethers, ethers, esters, alcohols, amides and/or water.
- the diluent should have a boiling point of at least 100° C., and preferably at least 200° C.
- the diluent as only one component or a combination of several ones, greatly determines the surface tension of the final ink, and thus it should have a surface tension within the print head requirements.
- dispersant it is often necessary to include a dispersant to effectively disperse the solid particles into the diluent and stabilize the dispersion.
- the dispersant must be capable of helping the process of grinding and stabilizing a dispersion of the solid in the required concentration into the chosen diluent at least under the operating conditions of the printing.
- Polymeric dispersants are preferred because of their efficiency.
- suitable dispersant are polyester amine dispersants (e.g. those sold by Lubrizol under the trade name of SOLSPERSE).
- dispersants that may be used are those marketed under the names EFKA and DISPERBYK. Mixtures of dispersants may be used if desired.
- dispersant For a given combination of diluent, dispersant and solid, the appropriate amount of dispersant may readily be determined by experiment.
- the ideal amount of dispersant is typically that which gives the minimum viscosity of the dispersion.
- the suitable amount of dispersant(s) varies depending on the specific surface area and the nature of the solid and will be found to lie in a very broad range, e.g. from about 5 to about 100% by weight of solid; larger amount of dispersant may be possible as well.
- the viscosity is determined largely by the viscosity of the diluent and the nature and concentration of the dispersant and solid. Generally, the typical viscosity range is from about 5 to about 50 mPa s, measured at the temperature of jetting.
- the dispersant is dissolved into the diluent and then the solid is added with stirring. After good dispersion is obtained, this slurry is milled using a conventional horizontal bead mill until the appropriate particle size distribution is obtained. The product is filtered to ensure that there is no coarse material or large agglomerates in the final suspension or inkjet composition.
- the solid component is a recently developed frit, which develops a matt effect (hereinafter sometimes referred to as a “matt frit”).
- the composition of the matt frit is shown in Table 1 below (weight percent):
- the matt frit once fired, exhibits a high resistance to chemical and physical attack. It also exhibits a high softening point. This allows the matt frit to not be attacked by conventional glazes, and the matt effect remains, essentially floating on the surface of the glazed tile. Decorative effects such as 3-D effects can thus be obtained. Furthermore, the matt frit does not modify substantially the color development of conventional ceramic pigment-containing inkjet inks.
- the inkjet composition was milled until a final fineness was obtained such that the 99th percentile (d99) was 2 ⁇ m.
- the inkjet composition was filtered throughout a 2.4 pm absolute filter.
- the inkjet composition exhibited the physical properties listed in Table 3 below:
- the inkjet composition was deposited on a ceramic substrate at a rate of approximately 10 g/m 2 . Once fired, the ceramic substrate exhibited a matt effect.
- Applicant has also developed an inkjet composition that provides a gloss effect when fired on the ceramic tile.
- the solid component of the inkjet composition is a frit, which develops a glossy surfaces on ceramic tiles (hereinafter sometimes referred to as a “gloss frit”).
- the composition of the gloss frit is shown in Table 4 below (weight percent):
- the gloss frit exhibits a low softening point, and does not produce surface defects on glazed ceramic surfaces, such as pinholes or bubbles, which are commonly associated with the use of excess flux. It does not substantially modify the color development of the conventional ceramic pigment-containing inkjet inks.
- An inkjet composition according to the invention was prepared with the composition shown in Table 5 below (parts by weight):
- the inkjet composition was milled until a final fineness was obtained such that the 99th percentile (d99) was 2 ⁇ m.
- the ink is filtered throughout a 2.4 ⁇ m absolute filter.
- the inkjet composition exhibited the physical properties listed in Table 6 below:
- the inkjet composition was deposited on a ceramic substrate at a rate of approximately 100 g/m 2 . Once fired, the ceramic substrate exhibited a glossy effect.
- Applicant has also developed an inkjet composition that provides an anti-slip effect when fired on the ceramic tile.
- the solid component of the inkjet composition comprises both a highly sintered a-alumina a glass frit.
- the crystals of highly sintered a-alumina are believed to be responsible for the high slip resistance.
- the glass frit is needed to provide proper bonding of the a-alumina crystals to the surface of the tile after firing.
- frit that can be used is the matt frit previously described above.
- An inkjet composition according to the invention was prepared with the composition shown in Table 7 below (parts by weight):
- the inkjet composition was milled until a final fineness was obtained such that the 99th percentile (d99) was 2 ⁇ m.
- the ink is filtered throughout a 2.4 ⁇ m absolute filter.
- the inkjet composition exhibited the physical properties listed in Table 8 below:
- the inkjet composition was deposited on a ceramic substrate at a rate of approximately 100 g/m 2 . Once fired, the ceramic substrate exhibited high slip resistance, when applied over a glossy glaze or a matt glaze. It also exhibited a smooth surface, high transparency, high acid resistance and did not substantially modify the color development of conventional ceramic pigment-containing inkjet inks.
- Table 9 summarizes the results of slip-resistance, acid resistance, and surface abrasion resistance of anti-slip ink compositions applied to matt and glossy glazes:
- Applicant has also developed an inkjet composition that provides a penetrating effect when fired on the ceramic tile.
- the following inkjet composition made in accordance with the present invention displays a penetrating effect on the surface of the ceramic tile after firing.
- the penetrating effect consists of a local depression of the surface of the ceramic tile. This penetrating effect is highly appreciated for decorative purposes.
- the solid component of the inkjet composition contains vanadium.
- the mechanism of the penetrating effect is associated with vanadium, which produces a lowering of the viscosity and surface tension of the melted glaze.
- the crystalline compound of vanadium may be any of the compounds described in “A” above.
- the frit preferably, is a fluxing frit with a composition in the following ranges as shown in Table 10 below (weight percent):
- An inkjet composition according to the invention was prepared with the composition shown in Table 12 below (parts by weight):
- the inkjet composition was milled until a final fineness was obtained such that the 99th percentile (d99) was 2 ⁇ m.
- the ink is filtered throughout a 2.4 ⁇ m absolute filter.
- the inkjet composition exhibited the physical properties listed in Table 13 below:
- the inkjet composition was deposited on a ceramic substrate at a rate of approximately 5 g/m 2 . Once fired, the ceramic substrate exhibited a penetrating effect.
- Applicant has also developed an inkjet composition that displays a luster effect on the substrate of the ceramic tile.
- Luster also called contrast gloss, is the gloss associated with contrast of bright and less bright adjacent areas of the surface of an object, due to differences in refractive index between layers.
- the solid component of the inkjet composition that displays a luster effect preferably contains tungsten. It has been found two types of formulations are suitable to produce a luster effect:
- An inkjet composition according to the invention was prepared with the composition shown in Table 14 below (parts by weight):
- the inkjet composition was milled until a final fineness was obtained such that the 99th percentile (d99) was 2 ⁇ m.
- the ink is filtered throughout a 2.4 ⁇ m absolute filter.
- the inkjet composition exhibited the physical properties listed in Table 15 below:
- the inkjet composition was deposited on a ceramic substrate at a rate of approximately 75 g/m 2 . Once fired, the ceramic substrate exhibited a luster effect.
- This inkjet composition is able to provide luster effect even at low deposition rates.
- the surface shows high transparency and does not interfere with the color development of the ceramic pigments commonly used.
- the X-ray characterization of the ceramic surface (see FIG. 2 ) showed that Scheelite crystals (CaWO4), were responsible for the luster effect.
- Applicant has also developed an inkjet composition that displays a metallic appearance on the substrate of the ceramic tile.
- a surface shows metallic appearance when the specular reflection is dominant over the diffuse reflection.
- the metallic appearance may be obtained with an inkjet composition that contains the inorganic components that, after firing, generate a crystallization responsible for this effect.
- the solid component of such an inkjet composition is ferric phosphate.
- a combination of ferric phosphate and a frit with high content of phosphorus may be used.
- the composition of the frit may be as shown in Table 16 below (weight percent):
- An inkjet composition according to the invention was prepared with the composition shown in Table 17 below (parts by weight):
- the inkjet composition was milled until a final fineness was obtained such that the 99th percentile (d99) was 2 ⁇ m.
- the ink is filtered throughout a 2.4 ⁇ m absolute filter.
- the inkjet composition exhibited the physical properties listed in Table 18 below:
- the inkjet composition was deposited on a ceramic substrate at a rate of approximately 75 g/m 2 . Once fired, the ceramic substrate exhibited a metallic effect.
Abstract
Description
- 1. Field of Invention
- The present invention provides inkjet compositions that can be used to modify the physical properties of the surface of glass and ceramic substrates and thus provide a functional coating or glaze after firing.
- 2. Description of Related Art
- It is conventional to apply colorants to ceramic substrates for decoration, and to apply glazes to obtain surface appearance effects. In recent years, much effort has been expended to obtain colorants that can be applied using inkjet application equipment. While these color-producing inks are suitable for their intended purpose, it would be advantageous if there were inkjet compositions that could be applied using conventional inkjet equipment to modify the appearance of the ceramic tile, while not interfering with the color development.
- The present invention provides inkjet compositions that can be used to modify the physical properties of the surface of glass and ceramic substrates and thus provide a functional coating or glaze after firing. The physical properties of the ceramic article that can be changed or modified with the inkjet compositions of the present invention can affect various attributes of the ceramic article after firing, including: gloss, matt, contrast gloss (luster), specular reflection (metallic appearance), relief and slipperiness.
- The inkjet compositions according to the invention include solvents, additives for dispersion, and inorganic substances. The inorganic substances contained in the inkjet compositions are the responsible for the above mentioned effects on the surface of the ceramic article. Depending on the type of effect desired, the inorganic substance may be a specific frit, a crystalline oxide, or a combination of frits and crystalline oxides.
- The inkjet compositions of the present invention may be used in conjunction with a variety of substrates including, for example: ceramic tiles (e.g., floor tile, wall tile etc.); dinnerware; brick tiles; glass; enameled steel; enameled cast iron; and enameled aluminum.
- The foregoing and other features of the invention are hereinafter more fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the present invention may be employed.
-
FIG. 1 is a chart showing various inkjet technologies suitable for use with inkjet compositions according to the invention. -
FIG. 2 is a graph showing the X-ray characterization of a ceramic tile to which an ink composition according to the invention has been applied. - Inkjet compositions according to the invention can be applied using inkjet decoration machines commonly used glazing lines of the above mentioned substrates. Also, inkjet plotter machines are commercially available, which permit the inkjet compositions to be used in a discontinuous way.
- Inkjet machines may be used in simple-pass or multi-pass operating mode. In the simple-pass mode, the inkjet print head makes only one-pass over the surface of the substrate. In the multi-pass mode, the inkjet print head makes more than one-pass over the surface of the substrate. In some cases, several passes are needed on order to achieve the desired properties.
- Many known types of inkjet print head technologies are suitable for use with inkjet compositions according to the present invention. Drop-on-demand technology is the most commonly employed technology in the ceramic industry. Various inkjet technologies suitable for use with the present invention are shown in
FIG. 1 . - Conventional inkjet compositions currently used on ceramic substrates, which are sometimes referred to in the art as “inks”, are utilized to provide coloration to the ceramic substrate when fired. For this purpose, conventional inkjet inks include solvents, dispersants and color-producing substances, which are typically ceramic pigments. The current ceramic pigments used in inkjet inks include zircon praseodymium yellow zircon, zinc iron chromite brown, cobalt aluminate blue, chrome tin pink sphene, iron cobalt chromite black spinel, etc.
- In contrast with the above mentioned inkjet inks, the inkjet compositions according to the present invention preferably do not contain any color-producing ceramic pigments. Instead, they contain inorganic substances that, although milled below 10 micron size so as to be capable of being ink-jet printable and being applied as very low deposits, are applied to modify targeted physical properties of the ceramic surface on which they are applied. Modification of the physical properties of the ceramic substrate can affect various attributes of the ceramic article after firing, including: gloss, matt, contrast gloss (luster), specular reflection (metallic appearance), relief and slipperiness.
- The use of inkjet technology provides the advantage of being able to apply the inkjet compositions in a determined place with high accuracy. So, the change of physical properties of the surface of the tile may follow an accurate pattern, opening new possibilities for tile decoration. It is seen as an advantage to combine the application of inkjet compositions according to the invention with the conventional pigmented inkjet inks. In this way, the ceramic article may be fully decorated using inkjet technology.
- One object of the present invention is to develop a set of inkjet compositions having a completely distinct nature compared to current pigmented inkjet inks. Inkjet compositions according to the invention are capable of being applied using conventional inkjet printing equipment without clogging the spray nozzles. Thus, the preferable have appropriate physical properties, such as a viscosity within the range of from about 5 to about 50 mPa·s, a surface tension of from about 20 to about 40 mN/m, and a density of from about 0.8 to about 1.5 g/mL. Advantageously, the inkjet compositions according to the invention preferably exhibit little or no volatility, and are stable with the materials used to make inkjet printing systems (e.g., print heads, nozzles, delivery lines etc.).
- In addition, it is advantageous for the inkjet compositions according to the invention to work with the requirements of ceramic systems. For example, they must be capable of developing the desired surface affect (i.e., the desired physical surface change) after firing. The must be capable of interacting with the glazed surface to become part of it. They must contain sufficient solids to allow reasonable productivity. And, they must allow for enough resolution despite the large amount to be deposited.
- The quantity of the inkjet compositions according to the invention deposited on the surface of the ceramic substrate will depend on the type of effect desired. The inkjet compositions according to the invention can be applied over a wide range of application rates, from about 5 up to about 500 g/m2, depending upon the desired affect. Typical application rates are used in the Examples below.
- Several affects can be obtained using the disclosed inkjet compositions. The affects are provided mainly by the presence of a particular solid in the inkjet composition. The inkjet composition contains a solvent or diluent, a dispersant and the solid that creates the effect.
- According to the present invention, the solid is dispersed in a solvent or diluent wherein the diluent is a single phase liquid comprising several solvents. This diluent can comprise aliphatic and/or aromatic hydrocarbon components as well as glycols, glycolethers, ethers, esters, alcohols, amides and/or water. In general, the diluent should have a boiling point of at least 100° C., and preferably at least 200° C. The diluent, as only one component or a combination of several ones, greatly determines the surface tension of the final ink, and thus it should have a surface tension within the print head requirements.
- It is often necessary to include a dispersant to effectively disperse the solid particles into the diluent and stabilize the dispersion. The dispersant must be capable of helping the process of grinding and stabilizing a dispersion of the solid in the required concentration into the chosen diluent at least under the operating conditions of the printing. Polymeric dispersants are preferred because of their efficiency. Examples of suitable dispersant are polyester amine dispersants (e.g. those sold by Lubrizol under the trade name of SOLSPERSE). Examples of other dispersants that may be used are those marketed under the names EFKA and DISPERBYK. Mixtures of dispersants may be used if desired.
- For a given combination of diluent, dispersant and solid, the appropriate amount of dispersant may readily be determined by experiment. The ideal amount of dispersant is typically that which gives the minimum viscosity of the dispersion. The suitable amount of dispersant(s) varies depending on the specific surface area and the nature of the solid and will be found to lie in a very broad range, e.g. from about 5 to about 100% by weight of solid; larger amount of dispersant may be possible as well.
- The viscosity is determined largely by the viscosity of the diluent and the nature and concentration of the dispersant and solid. Generally, the typical viscosity range is from about 5 to about 50 mPa s, measured at the temperature of jetting.
- The dispersant is dissolved into the diluent and then the solid is added with stirring. After good dispersion is obtained, this slurry is milled using a conventional horizontal bead mill until the appropriate particle size distribution is obtained. The product is filtered to ensure that there is no coarse material or large agglomerates in the final suspension or inkjet composition.
- The following examples are intended only to illustrate the invention and should not be construed as imposing limitations upon the claims.
- An inkjet composition according to the invention has been developed to provide a matt effect when fired on the ceramic tile. The solid component is a recently developed frit, which develops a matt effect (hereinafter sometimes referred to as a “matt frit”). The composition of the matt frit is shown in Table 1 below (weight percent):
-
TABLE 1 Al2O3 30-40% SiO2 40-60% MgO 10-20% - The matt frit, once fired, exhibits a high resistance to chemical and physical attack. It also exhibits a high softening point. This allows the matt frit to not be attacked by conventional glazes, and the matt effect remains, essentially floating on the surface of the glazed tile. Decorative effects such as 3-D effects can thus be obtained. Furthermore, the matt frit does not modify substantially the color development of conventional ceramic pigment-containing inkjet inks.
- An inkjet composition was been prepared with the composition shown in Table 2 below (parts by weight):
-
TABLE 2 Solid Matt frit 38.5 parts Dispersant SOLSPERSE 13940 7.7 parts Diluent Ruetasolv ZE-5050 45.8 parts Butyl diglyme 8.1 parts - The inkjet composition was milled until a final fineness was obtained such that the 99th percentile (d99) was 2 μm. The inkjet composition was filtered throughout a 2.4 pm absolute filter. The inkjet composition exhibited the physical properties listed in Table 3 below:
-
TABLE 3 Property T (° C.) Value Viscosity (mPa · s) 25.0 25.0 Density (g/mL) 25.0 1.303 Surface tension (mN/m) 25.0 32.9 - The inkjet composition was deposited on a ceramic substrate at a rate of approximately 10 g/m2. Once fired, the ceramic substrate exhibited a matt effect.
- Applicant has also developed an inkjet composition that provides a gloss effect when fired on the ceramic tile. The solid component of the inkjet composition is a frit, which develops a glossy surfaces on ceramic tiles (hereinafter sometimes referred to as a “gloss frit”). The composition of the gloss frit is shown in Table 4 below (weight percent):
-
TABLE 4 SiO2 50-60% B2O3 2-8% Al2O3 3-11% PbO 0-5% ZnO 2-8% BaO 1-5% MgO 0-2% CaO 5-15% Na2O, K2O 2-10% - The gloss frit exhibits a low softening point, and does not produce surface defects on glazed ceramic surfaces, such as pinholes or bubbles, which are commonly associated with the use of excess flux. It does not substantially modify the color development of the conventional ceramic pigment-containing inkjet inks.
- An inkjet composition according to the invention was prepared with the composition shown in Table 5 below (parts by weight):
-
TABLE 5 Solid Glossy frit 38.9 parts Dispersant SOLSPERSE 13940 7.8 parts Diluent Ruetasolv BP-4103 40.0 parts Butyl diglyme 13.0 parts - The inkjet composition was milled until a final fineness was obtained such that the 99th percentile (d99) was 2 μm. The ink is filtered throughout a 2.4 μm absolute filter. The inkjet composition exhibited the physical properties listed in Table 6 below:
-
TABLE 6 Property T (° C.) Value Viscosity (mPa · s) 25.0 27.5 Density (g/mL) 25.0 1.300 Surface tension (mN/m) 25.0 32.7 - The inkjet composition was deposited on a ceramic substrate at a rate of approximately 100 g/m2. Once fired, the ceramic substrate exhibited a glossy effect.
- Applicant has also developed an inkjet composition that provides an anti-slip effect when fired on the ceramic tile. The solid component of the inkjet composition comprises both a highly sintered a-alumina a glass frit. The crystals of highly sintered a-alumina are believed to be responsible for the high slip resistance. And the glass frit is needed to provide proper bonding of the a-alumina crystals to the surface of the tile after firing. An example of frit that can be used is the matt frit previously described above.
- An inkjet composition according to the invention was prepared with the composition shown in Table 7 below (parts by weight):
-
TABLE 7 Solid Sintered α-alumina 37.1 parts Matt frit 4.1 parts Dispersant SOLSPERSE 13940 7.4 parts diluents Ruetasolv BP-4201 34.8 parts Ruetasolv BP-4103 4.9 parts Exxsol D140 11.6 parts - The inkjet composition was milled until a final fineness was obtained such that the 99th percentile (d99) was 2 μm. The ink is filtered throughout a 2.4 μm absolute filter. The inkjet composition exhibited the physical properties listed in Table 8 below:
-
TABLE 8 Property T (° C.) Value Viscosity (mPa · s) 25.0 25.5 Density (g/mL) 25.0 1.273 Surface tension (mN/m) 25.0 31.6 - The inkjet composition was deposited on a ceramic substrate at a rate of approximately 100 g/m2. Once fired, the ceramic substrate exhibited high slip resistance, when applied over a glossy glaze or a matt glaze. It also exhibited a smooth surface, high transparency, high acid resistance and did not substantially modify the color development of conventional ceramic pigment-containing inkjet inks.
- Table 9 below summarizes the results of slip-resistance, acid resistance, and surface abrasion resistance of anti-slip ink compositions applied to matt and glossy glazes:
-
TABLE 9 Surface abrasion Slip resistance Acid resistance resistance according to ENV according to EN- according to EN- 12633 ISO 10545-13 ISO 10545-7 Glaze Rd KIND Acid Resistance PEI Matt Glaze 15 0 GHA V (control) Matt Glaze + 47 3 GHA V Anti-Slip Inkjet Composition Glossy Glaze 10 0 — — (control) Glossy Glaze + 36 2 GHA V Anti-Slip Inkjet Composition - Applicant has also developed an inkjet composition that provides a penetrating effect when fired on the ceramic tile. The following inkjet composition made in accordance with the present invention displays a penetrating effect on the surface of the ceramic tile after firing. The penetrating effect consists of a local depression of the surface of the ceramic tile. This penetrating effect is highly appreciated for decorative purposes.
- The solid component of the inkjet composition contains vanadium. The mechanism of the penetrating effect is associated with vanadium, which produces a lowering of the viscosity and surface tension of the melted glaze.
- It has been found three types of formulations provide this effect, namely:
-
- A. Formulations based on crystalline compounds of vanadium, like vanadium pentoxide, vanadium tetraoxide, sodium vanadate, bismuth vanadate, etc.
- B. A combination of crystalline compounds of vanadium and a frit.
- The crystalline compound of vanadium may be any of the compounds described in “A” above. The frit, preferably, is a fluxing frit with a composition in the following ranges as shown in Table 10 below (weight percent):
-
TABLE 10 SiO2 31-41% PbO 55-65% Al2O3 1-5% Na2O, K2O 0-2% -
- C. Formulation based on a vanadium containing frit, with a composition shown in Table 11 below (weight percent):
-
TABLE 11 SiO2 40-60% B2O3 5-20% Na2O, K2O 5-20% Li2O 0-5% V2O5 5-25% - An inkjet composition according to the invention was prepared with the composition shown in Table 12 below (parts by weight):
-
TABLE 12 Solid BiVO4 33.7 parts Dispersant SOLSPERSE 13940 6.1 parts Diluent Ruetasolv BP-4201 22.7 parts Ruetasolv BP-4103 27.4 parts Exxsol D140 10.1 parts - The inkjet composition was milled until a final fineness was obtained such that the 99th percentile (d99) was 2 μm. The ink is filtered throughout a 2.4 μm absolute filter. The inkjet composition exhibited the physical properties listed in Table 13 below:
-
TABLE 13 Property T (° C.) Value Viscosity (mPa · s) 25.0 26.8 Density (g/mL) 25.0 1.310 Surface tension (mN/m) 25.0 31.5 - The inkjet composition was deposited on a ceramic substrate at a rate of approximately 5 g/m2. Once fired, the ceramic substrate exhibited a penetrating effect.
- Applicant has also developed an inkjet composition that displays a luster effect on the substrate of the ceramic tile. Luster, also called contrast gloss, is the gloss associated with contrast of bright and less bright adjacent areas of the surface of an object, due to differences in refractive index between layers.
- The solid component of the inkjet composition that displays a luster effect preferably contains tungsten. It has been found two types of formulations are suitable to produce a luster effect:
-
- A. Formulations based on tungsten compounds like tungsten oxide, calcium tungstate, metallic tungsten, etc.
- B. Formulations based on a combination of a tungsten compound and a frit. The tungsten compound may be any of the compounds formerly described in “A” above. The frit is preferably a glossy frit, such as the gloss frit formerly described herein.
- An inkjet composition according to the invention was prepared with the composition shown in Table 14 below (parts by weight):
-
TABLE 14 Solid WO3 40.5 parts Dispersant SOLSPERSE 13940 7.3 parts Diluent Ruetasolv BP-4201 13.7 parts Ruetasolv BP-4103 26.1 parts Exxsol D140 12.4 parts - The inkjet composition was milled until a final fineness was obtained such that the 99th percentile (d99) was 2 μm. The ink is filtered throughout a 2.4 μm absolute filter. The inkjet composition exhibited the physical properties listed in Table 15 below:
-
TABLE 15 Property T (° C.) Value Viscosity (mPa · s) 25.0 33.0 Density (g/mL) 25.0 1.497 Surface tension (mN/m) 25.0 32.0 - The inkjet composition was deposited on a ceramic substrate at a rate of approximately 75 g/m2. Once fired, the ceramic substrate exhibited a luster effect.
- This inkjet composition is able to provide luster effect even at low deposition rates. At the same time, the surface shows high transparency and does not interfere with the color development of the ceramic pigments commonly used. The X-ray characterization of the ceramic surface (see
FIG. 2 ) showed that Scheelite crystals (CaWO4), were responsible for the luster effect. - Applicant has also developed an inkjet composition that displays a metallic appearance on the substrate of the ceramic tile. A surface shows metallic appearance when the specular reflection is dominant over the diffuse reflection. The metallic appearance may be obtained with an inkjet composition that contains the inorganic components that, after firing, generate a crystallization responsible for this effect.
- The solid component of such an inkjet composition is ferric phosphate. Also, a combination of ferric phosphate and a frit with high content of phosphorus may be used. The composition of the frit may be as shown in Table 16 below (weight percent):
-
TABLE 16 SiO2 30-45% Al2O3 5-20% P2O5 10-30% Li2O3 1-4% Na2O, K2O 5-15% CaO/MgO 5-15% - An inkjet composition according to the invention was prepared with the composition shown in Table 17 below (parts by weight):
-
TABLE 17 Solid FePO4 33.9 parts Dispersant SOLSPERSE 28000 8.8 parts Diluent Ruetasolv BP-4103 38.7 parts Butyl diglyme 18.6 parts - The inkjet composition was milled until a final fineness was obtained such that the 99th percentile (d99) was 2 μm. The ink is filtered throughout a 2.4 μm absolute filter. The inkjet composition exhibited the physical properties listed in Table 18 below:
-
TABLE 18 Property T (° C.) Value Viscosity (mPa · s) 25.0 27.4 Density (g/mL) 25.0 1.197 Surface tension (mN/m) 25.0 30.5 - The inkjet composition was deposited on a ceramic substrate at a rate of approximately 75 g/m2. Once fired, the ceramic substrate exhibited a metallic effect.
- Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and illustrative examples shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
Claims (23)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/911,107 US20130265376A1 (en) | 2013-06-06 | 2013-06-06 | Inkjet Compositions For Forming Functional Glaze Coatings |
PCT/US2014/037423 WO2014197165A1 (en) | 2013-06-06 | 2014-05-09 | Inkjet compositions for forming functional glaze coatings |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/911,107 US20130265376A1 (en) | 2013-06-06 | 2013-06-06 | Inkjet Compositions For Forming Functional Glaze Coatings |
Publications (1)
Publication Number | Publication Date |
---|---|
US20130265376A1 true US20130265376A1 (en) | 2013-10-10 |
Family
ID=49291970
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/911,107 Abandoned US20130265376A1 (en) | 2013-06-06 | 2013-06-06 | Inkjet Compositions For Forming Functional Glaze Coatings |
Country Status (2)
Country | Link |
---|---|
US (1) | US20130265376A1 (en) |
WO (1) | WO2014197165A1 (en) |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140044893A1 (en) * | 2012-08-13 | 2014-02-13 | Dip-Tech Ltd. | Glass panel |
CN103992695A (en) * | 2014-05-21 | 2014-08-20 | 佛山远牧数码科技有限公司 | Ceramic printing ink with crystallizing effect, and preparation and application methods thereof |
CN104403419A (en) * | 2014-12-04 | 2015-03-11 | 河北省沙河玻璃技术研究院 | Glass ink for ink-jet printing and preparation method of glass ink |
DE202015006002U1 (en) | 2014-07-14 | 2015-09-22 | Schott Ag | Ceramic ink-jet printing ink for low-expansion glass and / or low-expansion glass-ceramic |
US9446990B2 (en) | 2014-07-16 | 2016-09-20 | Electronics For Imaging, Inc. | Ceramic inkjet ink for relief effect |
WO2016172589A1 (en) * | 2015-04-24 | 2016-10-27 | Electronics For Imaging, Inc. | Method and apparatus for creating 3d effects with ceramic inkjet inks |
DE102015011750A1 (en) * | 2015-09-15 | 2017-03-16 | Durst Phototechnik Digital Technology Gmbh | Glaze stable mixture |
WO2017070236A1 (en) * | 2015-10-19 | 2017-04-27 | Electronics For Imaging, Inc. | Radiation-curable inkjet ink for application to glass, ceramic, or metal |
CN106800800A (en) * | 2016-01-28 | 2017-06-06 | 阿拉贡卡塔拉矿业股份有限公司 | For the pigment and ink of the decoration of ceramic articles |
EP3199506A1 (en) | 2016-01-28 | 2017-08-02 | Sociedad Anónima Minera Catalano-Aragonesa | Procedure for controlling the chemical reaction in multi-layer ceramic decorations |
US9822271B2 (en) | 2014-07-16 | 2017-11-21 | Electronics For Imaging, Inc. | Ceramic inkjet ink for red decoration |
US9868869B2 (en) | 2015-10-01 | 2018-01-16 | R.R. Donnelley & Sons Company | Ink composition for use on non-absorbent surfaces |
EP3299353A1 (en) | 2016-09-22 | 2018-03-28 | Sociedad Anónima Minera Catalano-Aragonesa | Ceramic glaze and ink composition for clear gloss ceramic coatings |
EP3327092A1 (en) | 2016-11-29 | 2018-05-30 | Sociedad Anónima Minera Catalano-Aragonesa | Transparent matt ink for the protection of ceramic coatings |
CN108503221A (en) * | 2018-04-20 | 2018-09-07 | 攀枝花学院 | Frit for porcelain enamel, enamel layer and preparation method thereof |
US10077370B2 (en) | 2014-09-26 | 2018-09-18 | Hewlett-Packard Development Company, L.P. | Non-Newtonian photo-curable ink composition |
US10077368B2 (en) | 2014-09-26 | 2018-09-18 | Hewlett-Packard Development Company, L.P. | Non-Newtonian photo-curable ink composition |
CN108976912A (en) * | 2018-07-18 | 2018-12-11 | 佛山市三水金鹰无机材料有限公司 | The preparation method of collapsible ink under a kind of pucherite |
CN109336393A (en) * | 2018-11-14 | 2019-02-15 | 宁波联城住工科技有限公司 | Anti-skidding glaze and preparation method thereof and a kind of production method of skid-resistance ceramic |
US10214651B2 (en) * | 2015-10-19 | 2019-02-26 | Merck Patent Gmbh | Pigment/frit mixtures |
US10392523B2 (en) | 2014-12-11 | 2019-08-27 | Hewlett-Packard Development Company, L.P. | Non-Newtonian photo-curable ink composition |
US10604667B2 (en) | 2014-06-26 | 2020-03-31 | Cryovac, Llc | Ink composition including polyurethane |
WO2020206843A1 (en) * | 2019-04-08 | 2020-10-15 | 东莞市唯美陶瓷工业园有限公司 | Silk-texture fine matte ceramic tile and preparation method therefor |
US10836195B2 (en) | 2018-10-08 | 2020-11-17 | Electronics For Imaging, Inc. | Inkjet process for three-dimensional relief on tiles |
US10844233B2 (en) | 2014-09-26 | 2020-11-24 | Hewlett-Packard Development Company, L.P. | Non-Newtonian photo-curable ink composition |
CN112429967A (en) * | 2020-12-11 | 2021-03-02 | 东莞市唯美陶瓷工业园有限公司 | Super-flat glaze for ceramic tiles, ceramic tiles and manufacturing method of ceramic tiles |
WO2021053250A1 (en) * | 2019-09-17 | 2021-03-25 | Sunic, S.L. | Inkjet inks comprising water soluble materials |
CN113501667A (en) * | 2021-08-12 | 2021-10-15 | 东莞市唯美陶瓷工业园有限公司 | Matt dry-particle glaze, digital ceramic ink and preparation method thereof |
CN113800767A (en) * | 2021-09-16 | 2021-12-17 | 蒙娜丽莎集团股份有限公司 | Transparent glaze with shell pearl luster and preparation method and application thereof |
CN113956714A (en) * | 2021-11-26 | 2022-01-21 | 山东国瓷康立泰新材料科技有限公司 | Matte finishing impression ink and preparation method and application thereof |
US11613666B2 (en) | 2019-10-17 | 2023-03-28 | Sun Inkjet Ceramics, S.L. | Inkjet inks for ceramic tile decoration |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107902905B (en) * | 2017-11-29 | 2020-12-01 | 佛山市华力达材料科技有限公司 | Production process of ceramic tile |
CN109516836B (en) * | 2018-11-27 | 2022-04-08 | 广西欧神诺陶瓷有限公司 | Preparation method of anti-slip ceramic tile |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU557059A1 (en) * | 1976-01-06 | 1977-05-05 | Государственный научно-исследовательский институт строительной керамики | Flux for ceramic paints |
BR9300519A (en) * | 1992-02-13 | 1993-08-17 | Lonza Ag | PARTICLES OF OXIDE-BASED MATERIAL AND PROCESS FOR ITS PREPARATION |
WO2005019360A1 (en) * | 2003-08-25 | 2005-03-03 | Dip Tech. Ltd. | Ink for ceramic surfaces |
DE102005040588B9 (en) * | 2004-08-20 | 2012-04-19 | Schott Ag | Use of a lead- and cadmium-free glass and method for glazing, enamelling and decorating of lithium aluminosilicate glass ceramics |
US20080036799A1 (en) * | 2005-03-25 | 2008-02-14 | Ittel Steven D | Processes for printing arrays of substantially parallel lines |
BY16275C1 (en) * | 2011-03-17 | 2012-08-30 |
-
2013
- 2013-06-06 US US13/911,107 patent/US20130265376A1/en not_active Abandoned
-
2014
- 2014-05-09 WO PCT/US2014/037423 patent/WO2014197165A1/en active Application Filing
Cited By (45)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140044893A1 (en) * | 2012-08-13 | 2014-02-13 | Dip-Tech Ltd. | Glass panel |
US8993102B2 (en) * | 2012-08-13 | 2015-03-31 | Dip-Tech Ltd. | Glass panel |
CN103992695A (en) * | 2014-05-21 | 2014-08-20 | 佛山远牧数码科技有限公司 | Ceramic printing ink with crystallizing effect, and preparation and application methods thereof |
US10604667B2 (en) | 2014-06-26 | 2020-03-31 | Cryovac, Llc | Ink composition including polyurethane |
DE202015006002U1 (en) | 2014-07-14 | 2015-09-22 | Schott Ag | Ceramic ink-jet printing ink for low-expansion glass and / or low-expansion glass-ceramic |
DE102014010335A1 (en) | 2014-07-14 | 2016-01-14 | Schott Ag | Ceramic ink-jet printing ink for glass and / or glass-ceramic, process for their preparation and use |
US9446990B2 (en) | 2014-07-16 | 2016-09-20 | Electronics For Imaging, Inc. | Ceramic inkjet ink for relief effect |
US9822271B2 (en) | 2014-07-16 | 2017-11-21 | Electronics For Imaging, Inc. | Ceramic inkjet ink for red decoration |
US10392524B2 (en) | 2014-07-16 | 2019-08-27 | Electronics For Imaging, Inc. | Ceramic inkjet ink for red decoration |
US10208220B2 (en) | 2014-09-26 | 2019-02-19 | Hewlett-Packard Development Company, L.P. | Non-Newtonian photo-curable ink composition |
US10077368B2 (en) | 2014-09-26 | 2018-09-18 | Hewlett-Packard Development Company, L.P. | Non-Newtonian photo-curable ink composition |
US10077370B2 (en) | 2014-09-26 | 2018-09-18 | Hewlett-Packard Development Company, L.P. | Non-Newtonian photo-curable ink composition |
US10844233B2 (en) | 2014-09-26 | 2020-11-24 | Hewlett-Packard Development Company, L.P. | Non-Newtonian photo-curable ink composition |
CN104403419A (en) * | 2014-12-04 | 2015-03-11 | 河北省沙河玻璃技术研究院 | Glass ink for ink-jet printing and preparation method of glass ink |
US10392523B2 (en) | 2014-12-11 | 2019-08-27 | Hewlett-Packard Development Company, L.P. | Non-Newtonian photo-curable ink composition |
CN107683211A (en) * | 2015-04-24 | 2018-02-09 | 图像电子公司 | The method and apparatus that 3D effect is created using ceramic ink jet ink |
EP3286007A4 (en) * | 2015-04-24 | 2019-01-02 | Electronics for Imaging, Inc. | Method and apparatus for creating 3d effects with ceramic inkjet inks |
US9630425B2 (en) | 2015-04-24 | 2017-04-25 | Electronics For Imaging, Inc. | Method and apparatus for creating 3D effects with ceramic inkjet inks |
WO2016172589A1 (en) * | 2015-04-24 | 2016-10-27 | Electronics For Imaging, Inc. | Method and apparatus for creating 3d effects with ceramic inkjet inks |
DE102015011750A1 (en) * | 2015-09-15 | 2017-03-16 | Durst Phototechnik Digital Technology Gmbh | Glaze stable mixture |
US9868869B2 (en) | 2015-10-01 | 2018-01-16 | R.R. Donnelley & Sons Company | Ink composition for use on non-absorbent surfaces |
US11008478B2 (en) | 2015-10-01 | 2021-05-18 | R. R. Donnelley & Sons Company | Ink composition for use on non-absorbent surfaces |
US9790388B2 (en) | 2015-10-19 | 2017-10-17 | Electronics For Imaging, Inc. | Radiation-curable inkjet ink for application to glass, ceramic, or metal |
WO2017070236A1 (en) * | 2015-10-19 | 2017-04-27 | Electronics For Imaging, Inc. | Radiation-curable inkjet ink for application to glass, ceramic, or metal |
US10214651B2 (en) * | 2015-10-19 | 2019-02-26 | Merck Patent Gmbh | Pigment/frit mixtures |
CN106800800A (en) * | 2016-01-28 | 2017-06-06 | 阿拉贡卡塔拉矿业股份有限公司 | For the pigment and ink of the decoration of ceramic articles |
EP3199594A1 (en) * | 2016-01-28 | 2017-08-02 | Sociedad Anónima Minera Catalano-Aragonesa | Pigment and ink for the decoration of ceramic objects |
EP3199506A1 (en) | 2016-01-28 | 2017-08-02 | Sociedad Anónima Minera Catalano-Aragonesa | Procedure for controlling the chemical reaction in multi-layer ceramic decorations |
US10259955B2 (en) * | 2016-01-28 | 2019-04-16 | Sociedad Anonima Minera Catalano Aragonesa | Pigment and ink for the decoration of ceramic objects |
US20170217845A1 (en) * | 2016-01-28 | 2017-08-03 | Sociedad Anonima Minera Catalano Aragonesa | Procedure for controlling the chemical reaction in multi-layer ceramic decorations |
EP3299353A1 (en) | 2016-09-22 | 2018-03-28 | Sociedad Anónima Minera Catalano-Aragonesa | Ceramic glaze and ink composition for clear gloss ceramic coatings |
EP3327092A1 (en) | 2016-11-29 | 2018-05-30 | Sociedad Anónima Minera Catalano-Aragonesa | Transparent matt ink for the protection of ceramic coatings |
CN108503221A (en) * | 2018-04-20 | 2018-09-07 | 攀枝花学院 | Frit for porcelain enamel, enamel layer and preparation method thereof |
CN108976912A (en) * | 2018-07-18 | 2018-12-11 | 佛山市三水金鹰无机材料有限公司 | The preparation method of collapsible ink under a kind of pucherite |
US10836195B2 (en) | 2018-10-08 | 2020-11-17 | Electronics For Imaging, Inc. | Inkjet process for three-dimensional relief on tiles |
CN113195232A (en) * | 2018-10-08 | 2021-07-30 | 图像电子公司 | Inkjet treatment of three-dimensional relief on ceramic tiles |
US11633972B2 (en) | 2018-10-08 | 2023-04-25 | Electronics For Imaging, Inc. | Inkjet process for three-dimensional relief on tiles |
CN109336393A (en) * | 2018-11-14 | 2019-02-15 | 宁波联城住工科技有限公司 | Anti-skidding glaze and preparation method thereof and a kind of production method of skid-resistance ceramic |
WO2020206843A1 (en) * | 2019-04-08 | 2020-10-15 | 东莞市唯美陶瓷工业园有限公司 | Silk-texture fine matte ceramic tile and preparation method therefor |
WO2021053250A1 (en) * | 2019-09-17 | 2021-03-25 | Sunic, S.L. | Inkjet inks comprising water soluble materials |
US11613666B2 (en) | 2019-10-17 | 2023-03-28 | Sun Inkjet Ceramics, S.L. | Inkjet inks for ceramic tile decoration |
CN112429967A (en) * | 2020-12-11 | 2021-03-02 | 东莞市唯美陶瓷工业园有限公司 | Super-flat glaze for ceramic tiles, ceramic tiles and manufacturing method of ceramic tiles |
CN113501667A (en) * | 2021-08-12 | 2021-10-15 | 东莞市唯美陶瓷工业园有限公司 | Matt dry-particle glaze, digital ceramic ink and preparation method thereof |
CN113800767A (en) * | 2021-09-16 | 2021-12-17 | 蒙娜丽莎集团股份有限公司 | Transparent glaze with shell pearl luster and preparation method and application thereof |
CN113956714A (en) * | 2021-11-26 | 2022-01-21 | 山东国瓷康立泰新材料科技有限公司 | Matte finishing impression ink and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
WO2014197165A1 (en) | 2014-12-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20130265376A1 (en) | Inkjet Compositions For Forming Functional Glaze Coatings | |
EP2843011B1 (en) | Digital enamel ink | |
EP3848422B1 (en) | Manufacturing decorative panels | |
EP2826825B1 (en) | Ceramic inkjet inks | |
JP4893080B2 (en) | Decorative ceramic body | |
US20160280588A1 (en) | Inkjet Compositions For Forming Functional Glaze Coatings | |
CN105153809A (en) | Glass ink-jet printing ink | |
CN107849374A (en) | For the dispersant using jetted ink coloring ceramic tile | |
JP7122057B2 (en) | Particle mixtures, kits, inks, methods and articles | |
JP4075864B2 (en) | Decorative ceramic body, manufacturing method thereof and glaze preparation | |
EP2818523A1 (en) | Ink composition for decorating non-porous substrates | |
EP3199594B1 (en) | Pigment and ink for the decoration of ceramic objects | |
JP6381969B2 (en) | Inkjet printing method | |
EP4015591A1 (en) | Inkjet inks for ceramic tile decoration | |
JP2008222962A (en) | Inorganic pigment, its manufacturing method, ink for inkjet, decorative ceramic, and its manufacturing method | |
JP6764260B2 (en) | Manufacturing method of printed matter, glaze for forming printed matter, and printed matter | |
EP3144357A1 (en) | Magenta ink composition for decorating non-porous substrates | |
US20190224990A1 (en) | Process for preparing decorative fired substrate | |
EP3988623A1 (en) | Inkjet inks comprising water soluble materials | |
WO2015046020A1 (en) | Inkjet ink set, method for producing inkjet printed material using same, and inkjet printed material | |
TW202336177A (en) | Inkjet printable inks for fabricating enamel coatings | |
WO2005082811A1 (en) | Method for decorating ceramic substrates by applying printing agents prior to dyeing, compositions used and dyeing compositions compatible with said method | |
CN107987614A (en) | A kind of ink of inkjet printing and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: FERRO CORPORATION, OHIO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GIL-TORRENTE, ANA-BELEN;SILVESTRE-LASA, EUGENIO;GUAITA-DELGADO, FRANCISCO-JAVIER;AND OTHERS;SIGNING DATES FROM 20130612 TO 20130613;REEL/FRAME:030724/0730 |
|
AS | Assignment |
Owner name: PNC BANK, NATIONAL ASSOCIATION, PENNSYLVANIA Free format text: PATENT SECURITY AGREEMENT;ASSIGNOR:FERRO CORPORATION;REEL/FRAME:033522/0966 Effective date: 20140731 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |
|
AS | Assignment |
Owner name: FERRO CORPORATION, OHIO Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:PNC BANK, NATIONAL ASSOCIATION, AS COLLATERAL AGENT;REEL/FRAME:041718/0307 Effective date: 20170214 |
|
AS | Assignment |
Owner name: PNC BANK, NATIONAL ASSOCIATION, AS COLLATERAL AGENT, PENNSYLVANIA Free format text: SECURITY INTEREST;ASSIGNOR:FERRO CORPORATION;REEL/FRAME:041736/0178 Effective date: 20170214 Owner name: PNC BANK, NATIONAL ASSOCIATION, AS COLLATERAL AGEN Free format text: SECURITY INTEREST;ASSIGNOR:FERRO CORPORATION;REEL/FRAME:041736/0178 Effective date: 20170214 |
|
AS | Assignment |
Owner name: FERRO CORPORATION, OHIO Free format text: RELEASE OF SECURITY INTEREST IN PATENTS RECORDED AT R/F 041736/0178;ASSIGNOR:PNC BANK NATIONAL ASSOCIATION, AS COLLATERAL AGENT;REEL/FRAME:059747/0129 Effective date: 20220421 |